In the title compound, C(36)H(25)F(6)O(2)P(2)(+)·I(3)(-), hydrogen-bonded [{(p-FC(6)H(4))(3)PO}(2)H](+) dimers assemble along the crystallographic c axis to form channels that house extended chains of triiodide anions. Although the I-I bond lengths of 2.9452 (14) and 2.9023 (15) Å are typical, the inter-ion I...I distance of 3.5774 (10) Å is unusually short. A posteriori modelling of nonmerohedral twinning about (100) has been only partially successful, achieving a reduction in the maximum residual electron density from 5.28 to 3.24 e Å(-3). The inclusion of two low-occupancy I-atom sites (total 1.7%), which can be interpreted as translational disorder of the triiodide anions along the channels, reduced the maximum residual electron density to 2.03 e Å(-3). The minor fractional contribution volume of the nonmerohedral twin domains refined to 0.24 and simultaneous refinement of the inversion twin domains showed the crystal to be a 0.5:0.5 inversion twin.
In the crystal structure of the title compound, 2C(22)H(24)P(+)·I(8)(2-), the I(8)(2-) anion is located on a crystallographic inversion centre and consists of two tri-iodide anions linked by di-iodine at angles of 89.92 4)° to form a planar `Z'-shaped dianion. The octaiodides are linked via long-range interactions [3.877 11) ] into infinite polyiodide ribbons. This is the first example of a structure containing an [(o-tolyl)(3)PMe](+) cation, and the C(Me)-P-C-C(Me) torsion angles of -54.0 11), -51.3 11) and -48.2 11)° indicate that the configuration is exo(3).
The Cu(II) complex bis[hydroxybis(pyridin-2-yl)methanesulfonato-κ(3)N,O,N']copper(II) hexahydrate, [Cu(C(11)H(9)N(2)O(4)S)(2)]·6H(2)O, (I), crystallizes in the space group P1, compared with P2(1)/c for the anhydrous Co(II) analogue bis[hydroxybis(pyridin-2-yl)methanesulfonato-κ(3)N,O,N']cobalt(II), [Co(C(11)H(9)N(2)O(4)S)(2)], (II). However, both molecules sit on a crystallographic inversion centre and are thus very similar in appearance. Jahn-Teller elongation of the Cu-O bonds [2.347 (3) Å in (I) and 2.064 (2) Å in (II)] influences the S-O bond lengths, which are all around 1.455 (3) Å in (I) and 1.436 (2)-1.473 (2) Å in (II).
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